Negative ion antibacterial polyester fiber composite fabric and production process thereof

Abstract

The invention discloses a negative ion antibacterial polyester fiber composite fabric and a production process thereof.The composite fabric comprises modified base cloth, a reinforced antibacterial layer and a protective layer, the composite fabric is of a multi-layer antibacterial structure, the modified base cloth contains tourmaline powder, the tourmaline powder contains a large number of negative ions, and the protective layer is made of polyester fibers. The negative ions can change cell wall structures and cell membrane functions of bacteria, further destroy life activities of microorganisms, and combine with biomolecules such as proteins, nucleic acids and enzymes in the bacteria to denature, solidify or inactivate the biomolecules, thereby causing death of the bacteria. A terpyridyl structure on the surface of the modified base cloth and a terpyridyl structure in the modified ligand are matched with neodymium trichloride hexahydrate, and a rare earth complex of pyridine neodymium is formed on the surface of the modified base cloth and is matched with benzimidazolyl pyridinium on the surface, so that the antibacterial efficiency is greatly improved.

Description

Technical Field

[0001] The invention relates to the technical field of antibacterial fabric preparation, and in particular to a negative ion antibacterial polyester fiber composite fabric and a production process thereof. Background Art

[0002] As a synthetic fiber widely used in the textile industry, polyester fiber has the advantages of good wear resistance, wrinkle resistance, and moisture absorption and perspiration. However, its defects such as easy adsorption of odor and breeding of bacteria restrict its application in specific fields, such as medical treatment, food processing, sportswear, etc. In recent years, people have paid more and more attention to the antibacterial function of materials and sought more effective, safer and environmentally friendly antibacterial methods. Negative ion materials have attracted widespread attention due to their unique antibacterial properties. Negative ions can interact with the positive charges on the bacterial cell membrane, destroy the structure and function of the cell membrane, and thus achieve an antibacterial effect. However, as the fabric is used for a long time and washed many times, the antibacterial effect decreases significantly, thereby shortening the service life. Summary of the invention

[0003] The purpose of the present invention is to provide a negative ion antibacterial polyester fiber composite fabric and a production process thereof, which solves the problem that the antibacterial effect of the current polyester fiber composite fabric is general and the antibacterial effect is significantly reduced after repeated washing.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A production process of negative ion antibacterial polyester fiber composite fabric, specifically comprising the following steps:

[0006] Step A1: evenly mix o-aminothiophenol, 4-pyridinecarboxaldehyde, ammonium chloride and ethanol, and react for 20-25 hours at a speed of 120-150 r / min and a temperature of 60-65° C. to obtain intermediate 1; evenly mix intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile, and react for 3-5 hours at a speed of 200-300 r / min and a temperature of 70-75° C. to obtain an antibacterial monomer; evenly mix intermediate 2, acrylic acid chloride, potassium carbonate and acetone, and react for 10-15 hours at a speed of 60-80 r / min and a temperature of 60-65° C. to obtain a modified ligand;

[0007] Step A2: dissolving the modified ligand in ethanol, soaking the modified base fabric therein, ultrasonically treating for 5-10 min at a frequency of 20-30 kHz, a temperature of 60-65° C., and a pH value of 7.5-8, adding neodymium trichloride hexahydrate, ultrasonically treating for 5-7 h, taking out and drying, forming a reinforced antibacterial layer on the surface of the modified base fabric, and obtaining a pretreated base fabric;

[0008] Step A3: evenly mix the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane and ethanol, immerse the pretreated base fabric therein, perform ultrasonic treatment for 5-10 min at a frequency of 20-30 kHz and a temperature of 20-25°C, add potassium persulfate, perform ultrasonic treatment for 3-5 min, take out the pretreated base fabric, perform heat preservation treatment for 2-3 h at a temperature of 70-75°C, form a protective layer on the surface of the pretreated base fabric, and obtain a negative ion antibacterial polyester fiber composite fabric.

[0009] Furthermore, the molar ratio of o-aminothiophenol, 4-pyridinecarboxaldehyde and ammonium chloride in step A1 is 3:3:1, the usage ratio of intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile is 1 mmol:1 mmol:8 mL, and the molar ratio of intermediate 2, acrylic acid chloride and potassium carbonate is 1:1:1.1.

[0010] Furthermore, the usage ratio of the modified ligand, ethanol and neodymium chloride hexahydrate described in step A2 is 5 mmol:10 mL:3 mmol.

[0011] Furthermore, the amount ratio of the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane, ethanol and potassium persulfate described in step A3 is 2.3g:18g:20g:1.2g:120mL:0.1g.

[0012] Further, the modified base fabric is made by the following steps:

[0013] Step B1: p-Hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and ammonia water are mixed, and the mixture is reacted for 8-10 hours at a speed of 120-150 r / min and a temperature of 50-55° C. to obtain intermediate 2; intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone are uniformly mixed, and the mixture is reacted for 10-15 hours at a speed of 60-80 r / min and a temperature of 60-65° C. to obtain intermediate 3; intermediate 3, sodium methoxide, ethanol and tetrahydrofuran are mixed, nitrogen is introduced for protection, and the mixture is reacted for 2-3 hours at a speed of 200-300 r / min and a temperature of 20-25° C. to obtain a modifier;

[0014] Step B2: uniformly mix the modifier, itaconic acid, benzoin dimethyl ether and DMF, and react for 1-1.5 hours at a speed of 60-80 r / min, a temperature of 20-25° C. and irradiation with 365 nm ultraviolet light to obtain a modified monomer; uniformly mix terephthalic acid, the modified monomer, ethylene glycol, antimony trioxide and triphenyl phosphite, and react for 1-2 hours at a speed of 60-80 r / min and a temperature of 170-180° C., and heat to 235-240° C., and react for 3-5 hours at a vacuum degree of 0.3-0.5 MPa, and heat to 270-280° C., and react for 20-30 minutes at a vacuum degree of 80-90 Pa to obtain a modified polyester;

[0015] Step B3: The modified polyester and tourmaline powder are mixed and added into an extruder, melt-extruded and spun at a temperature of 280-290°C to obtain polyester fiber, and the polyester fiber and cotton fiber are subjected to cotton grabbing, cotton blending, cotton opening, cotton feeding, cotton rolling, cotton carding, cotton drawing and roving treatment to obtain composite roving, and the composite roving is weft-knitted with double rib to obtain a modified base cloth.

[0016] Furthermore, the amount ratio of p-hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and ammonia water described in step B1 is 4mmol:8mmol:15mmol:20mL:10mL, the mass fraction of ammonia water is 30%, the amount ratio of intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone is 5mmol:5mmol:10mmol:40mL, and the amount ratio of intermediate 3, sodium methoxide, ethanol and tetrahydrofuran is 1mmol:2mmol:2mL:2mL.

[0017] Furthermore, the molar ratio of the modifier and itaconic acid described in step B2 is 1:1, the amount of benzoin dimethyl ether is 1% of the total mass of the modifier and itaconic acid, the molar ratio of phthalic acid, modified monomer and ethylene glycol is 1.5:0.5:2.4, the amount of antimony trioxide is 1‰ of the mass of phthalic acid and modified monomer, and the amount of triphenyl phosphite is 1‰ of the mass of phthalic acid and modified monomer.

[0018] Furthermore, the mass ratio of the modified polyester and tourmaline powder in step B3 is 100:8-10, and the mass ratio of the polyester fiber and the cotton fiber is 4:3.

[0019] Beneficial effects of the present invention: A negative ion antibacterial polyester fiber composite fabric disclosed by the present invention comprises the following steps: dissolving a modified ligand in ethanol, soaking the modified base fabric therein, ultrasonically treating it, adding neodymium chloride hexahydrate, taking it out after ultrasonic treatment and drying it, forming a reinforced antibacterial layer on the surface of the modified base fabric to prepare a pretreated base fabric, uniformly mixing antibacterial monomers, methyl methacrylate, n-butyl acrylate, tetravinylsilane and ethanol, soaking the pretreated base fabric therein, ultrasonically treating it, adding potassium persulfate, taking out the pretreated base fabric after ultrasonic treatment, and drying it. The cloth is subjected to heat preservation treatment to form a protective layer on the surface of the pretreated base cloth to obtain a negative ion antibacterial polyester fiber composite fabric, the modified monomer is reacted with o-aminothiophenol and 4-pyridinecarboxaldehyde to form a thiazole structure to obtain an intermediate 1, the intermediate 1 is reacted with ethyl 2-bromomethylacrylate to make the pyridine on the intermediate 1 react with the bromine atom site on the ethyl 2-bromomethylacrylate to obtain an antibacterial monomer, the intermediate 2 is reacted with acryloyl chloride to make the phenolic hydroxyl group on the intermediate 2 react with the acyl chloride group on the acryloyl chloride to obtain a modified ligand.

[0020] The modified base fabric uses p-hydroxybenzaldehyde and 2-acetylpyridine as raw materials to react to form a terpyridine structure to obtain intermediate 2, and reacts intermediate 2 with S-(2-bromoethyl)ethylthioate so that the hydroxyl group in intermediate 2 reacts with the bromine atom site on S-(2-bromoethyl)ethylthioate to obtain intermediate 3, and treats intermediate 3 with sodium methoxide to convert the thioate on intermediate 3 into a thiol group to obtain a modifier, and the modifier and itaconic acid are reacted in an aqueous solution. Under the action of benzoin dimethyl ether, the mercapto group on the modifier and the double bond on itaconic acid react to obtain a modified monomer, terephthalic acid, the modified monomer and ethylene glycol are esterified and condensed to obtain a modified polyester, the modified polyester and tourmaline powder are mixed and melt-spun to obtain polyester fiber, the polyester fiber and cotton fiber are subjected to cotton grabbing, cotton blending, cotton opening, cotton feeding, cotton rolling, cotton carding, cotton drawing and roving treatment to obtain a composite roving, the composite roving is weft-knitted double rib weave to obtain a modified base cloth.

[0021] The composite fabric has a multi-layer antibacterial structure, wherein the modified base fabric contains tourmaline powder, which contains a large amount of negative ions. The negative ions can change the bacterial cell wall structure and cell membrane function, thereby destroying the life activities of microorganisms, and combine with biological molecules such as proteins, nucleic acids and enzymes in bacteria to denature, coagulate or inactivate them, thereby causing the death of bacteria. When the modified base fabric is immersed in a modified ligand ethanol solution, neodymium trichloride hexahydrate is added, and the terpyridine structure on the surface of the modified base fabric and the terpyridine structure in the modified ligand cooperate with the neodymium trichloride hexahydrate to form a rare earth complex of neodymium pyridine on the surface of the modified base fabric. , then the pretreated base fabric is immersed in a mixture of antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinyl silane and ethanol, potassium persulfate is added, and the pretreated base fabric is taken out. During the heat preservation process, the double bonds on the surface of the pretreated base fabric will polymerize with the antibacterial monomer, methyl methacrylate, n-butyl acrylate and tetravinyl silane to form a polyacrylate structure on the surface of the reinforced antibacterial layer. The polyacrylate structure contains benzimidazolyl pyridinium salt, which can interact electrostatically with bacteria, causing damage to the cell wall structure and leakage of cell contents. Combined with the rare earth complex, the antibacterial efficiency is greatly improved. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Embodiment 1: A production process of a negative ion antibacterial polyester fiber composite fabric, comprising the following steps:

[0024] Step A1: evenly mix o-aminothiophenol, 4-pyridinecarboxaldehyde, ammonium chloride and ethanol, and react at a speed of 120 r / min and a temperature of 60° C. for 20 hours to obtain intermediate 1; evenly mix intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile, and react at a speed of 200 r / min and a temperature of 70° C. for 3 hours to obtain an antibacterial monomer; evenly mix intermediate 2, acrylic acid chloride, potassium carbonate and acetone, and react at a speed of 60 r / min and a temperature of 60° C. for 10 hours to obtain a modified ligand;

[0025] Step A2: dissolving the modified ligand in ethanol, soaking the modified base fabric therein, ultrasonically treating for 5 min at a frequency of 20 kHz, a temperature of 60° C., and a pH value of 7.5, adding neodymium trichloride hexahydrate, and ultrasonically treating for 5 h, taking out and drying, forming a reinforced antibacterial layer on the surface of the modified base fabric, and obtaining a pretreated base fabric;

[0026] Step A3: evenly mix the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane and ethanol, immerse the pretreated base fabric therein, perform ultrasonic treatment for 5 min at a frequency of 20 kHz and a temperature of 20°C, add potassium persulfate, perform ultrasonic treatment for 3 min, take out the pretreated base fabric, perform heat preservation treatment for 2 h at a temperature of 70°C, form a protective layer on the surface of the pretreated base fabric, and obtain a negative ion antibacterial polyester fiber composite fabric.

[0027] The molar ratio of o-aminothiophenol, 4-pyridinecarboxaldehyde and ammonium chloride in step A1 is 3:3:1, the usage ratio of intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile is 1 mmol:1 mmol:8 mL, and the molar ratio of intermediate 2, acrylic acid chloride and potassium carbonate is 1:1:1.1.

[0028] The amount ratio of the modified ligand, ethanol and neodymium trichloride hexahydrate described in step A2 is 5mmo l:10mL:3mmol.

[0029] The amount ratio of the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane, ethanol and potassium persulfate described in step A3 is 2.3g:18g:20g:1.2g:120mL:0.1g.

[0030] The modified base fabric is made by the following steps:

[0031] Step B1: p-Hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and aqueous ammonia are mixed, and the mixture is reacted at a speed of 120 r / min and a temperature of 50° C. for 8 h to obtain intermediate 2; intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone are uniformly mixed, and the mixture is reacted at a speed of 60 r / min and a temperature of 60° C. for 10 h to obtain intermediate 3; intermediate 3, sodium methoxide, ethanol and tetrahydrofuran are mixed, nitrogen is introduced for protection, and the mixture is reacted at a speed of 200 r / min and a temperature of 20° C. for 2 h to obtain a modifier;

[0032] Step B2: the modifier, itaconic acid, benzoin dimethyl ether and DMF are mixed uniformly, and the reaction is carried out for 1 hour at a speed of 60 r / min, a temperature of 20° C. and irradiation with 365 nm ultraviolet light to obtain a modified monomer; terephthalic acid, the modified monomer, ethylene glycol, antimony trioxide and triphenyl phosphite are mixed uniformly, and the reaction is carried out for 1 hour at a speed of 60 r / min and a temperature of 170° C., and the temperature is raised to 235° C. and the reaction is carried out for 3 hours at a vacuum degree of 0.3 MPa, and the temperature is raised to 270° C. and the reaction is carried out for 20 minutes at a vacuum degree of 80 Pa to obtain a modified polyester;

[0033] Step B3: The modified polyester and tourmaline powder are mixed and added into an extruder, melt-extruded and spun at a temperature of 280°C to obtain polyester fiber, and the polyester fiber and cotton fiber are subjected to cotton grabbing, cotton blending, cotton opening, cotton feeding, cotton rolling, cotton carding, cotton drawing and roving treatment to obtain composite roving, and the composite roving is weft-knitted with double rib to obtain a modified base cloth.

[0034] The amount ratio of p-hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and ammonia water described in step B1 is 4mmol:8mmol:15mmol:20mL:10mL, the mass fraction of ammonia water is 30%, the amount ratio of intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone is 5mmol:5mmol:10mmol:40mL, and the amount ratio of intermediate 3, sodium methoxide, ethanol and tetrahydrofuran is 1mmol:2mmol:2mL:2mL.

[0035] The molar ratio of the modifier and itaconic acid described in step B2 is 1:1, the amount of benzoin dimethyl ether is 1% of the total mass of the modifier and itaconic acid, the molar ratio of phthalic acid, modified monomer and ethylene glycol is 1.5:0.5:2.4, the amount of antimony trioxide is 1‰ of the mass of phthalic acid and modified monomer, and the amount of triphenyl phosphite is 1‰ of the mass of phthalic acid and modified monomer.

[0036] The mass ratio of the modified polyester and tourmaline powder described in step B3 is 100:8, and the mass ratio of the polyester fiber and the cotton fiber is 4:3.

[0037] Embodiment 2: A production process of a negative ion antibacterial polyester fiber composite fabric, comprising the following steps:

[0038] Step A1: evenly mix o-aminothiophenol, 4-pyridinecarboxaldehyde, ammonium chloride and ethanol, and react at a speed of 120 r / min and a temperature of 65° C. for 20 hours to obtain intermediate 1; evenly mix intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile, and react at a speed of 300 r / min and a temperature of 70° C. for 4 hours to obtain an antibacterial monomer; evenly mix intermediate 2, acrylic acid chloride, potassium carbonate and acetone, and react at a speed of 60 r / min and a temperature of 65° C. for 10 hours to obtain a modified ligand;

[0039] Step A2: dissolving the modified ligand in ethanol, soaking the modified base fabric therein, ultrasonically treating the base fabric for 5 min at a frequency of 25 kHz, a temperature of 60° C., and a pH value of 8, adding neodymium trichloride hexahydrate, and ultrasonically treating the base fabric for 6 h, then taking the base fabric out and drying the same to form a reinforced antibacterial layer on the surface of the modified base fabric, thereby obtaining a pretreated base fabric;

[0040] Step A3: Evenly mix the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane and ethanol, immerse the pretreated base fabric therein, perform ultrasonic treatment for 5 min at a frequency of 25 kHz and a temperature of 25°C, add potassium persulfate, perform ultrasonic treatment for 4 min, take out the pretreated base fabric, perform heat preservation treatment for 3 h at a temperature of 70°C, form a protective layer on the surface of the pretreated base fabric, and obtain a negative ion antibacterial polyester fiber composite fabric.

[0041] The molar ratio of o-aminothiophenol, 4-pyridinecarboxaldehyde and ammonium chloride in step A1 is 3:3:1, the usage ratio of intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile is 1 mmol:1 mmol:8 mL, and the molar ratio of intermediate 2, acrylic acid chloride and potassium carbonate is 1:1:1.1.

[0042] The usage ratio of the modified ligand, ethanol and neodymium trichloride hexahydrate described in step A2 is 5 mmol:10 mL:3 mmol.

[0043] The amount ratio of the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane, ethanol and potassium persulfate described in step A3 is 2.3g:18g:20g:1.2g:120mL:0.1g.

[0044] The modified base fabric is made by the following steps:

[0045] Step B1: p-Hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and aqueous ammonia are mixed, and the mixture is reacted at a speed of 120 r / min and a temperature of 55° C. for 9 hours to obtain intermediate 2; intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone are uniformly mixed, and the mixture is reacted at a speed of 60 r / min and a temperature of 65° C. for 10 hours to obtain intermediate 3; intermediate 3, sodium methoxide, ethanol and tetrahydrofuran are mixed, nitrogen is introduced for protection, and the mixture is reacted at a speed of 300 r / min and a temperature of 20° C. for 3 hours to obtain a modifier;

[0046] Step B2: The modifier, itaconic acid, benzoin dimethyl ether and DMF are mixed uniformly, and the reaction is carried out for 1.5 hours at a speed of 60 r / min, a temperature of 25° C. and irradiation with 365 nm ultraviolet light to obtain a modified monomer; terephthalic acid, the modified monomer, ethylene glycol, antimony trioxide and triphenyl phosphite are mixed uniformly, and the reaction is carried out for 1.5 hours at a speed of 60 r / min and a temperature of 175° C., and the temperature is raised to 235° C., and the reaction is carried out for 4 hours at a vacuum degree of 0.4 MPa, and the temperature is raised to 275° C., and the reaction is carried out for 25 minutes at a vacuum degree of 85 Pa to obtain a modified polyester;

[0047] Step B3: The modified polyester and tourmaline powder are mixed and added into an extruder, melt-extruded and spun at a temperature of 280-290°C to obtain polyester fiber, and the polyester fiber and cotton fiber are subjected to cotton grabbing, cotton blending, cotton opening, cotton feeding, cotton rolling, cotton carding, cotton drawing and roving treatment to obtain composite roving, and the composite roving is weft-knitted with double rib to obtain a modified base cloth.

[0048] The amount ratio of p-hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and ammonia water described in step B1 is 4mmol:8mmol:15mmol:20mL:10mL, the mass fraction of ammonia water is 30%, the amount ratio of intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone is 5mmol:5mmol:10mmol:40mL, and the amount ratio of intermediate 3, sodium methoxide, ethanol and tetrahydrofuran is 1mmol:2mmol:2mL:2mL.

[0049] The molar ratio of the modifier and itaconic acid described in step B2 is 1:1, the amount of benzoin dimethyl ether is 1% of the total mass of the modifier and itaconic acid, the molar ratio of phthalic acid, modified monomer and ethylene glycol is 1.5:0.5:2.4, the amount of antimony trioxide is 1‰ of the mass of phthalic acid and modified monomer, and the amount of triphenyl phosphite is 1‰ of the mass of phthalic acid and modified monomer.

[0050] The mass ratio of the modified polyester and tourmaline powder described in step B3 is 100:9, and the mass ratio of the polyester fiber and the cotton fiber is 4:3.

[0051] Embodiment 3: A production process of a negative ion antibacterial polyester fiber composite fabric, comprising the following steps:

[0052] Step A1: evenly mix o-aminothiophenol, 4-pyridinecarboxaldehyde, ammonium chloride and ethanol, and react at a speed of 150 r / min and a temperature of 65° C. for 25 hours to obtain intermediate 1; evenly mix intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile, and react at a speed of 300 r / min and a temperature of 75° C. for 5 hours to obtain an antibacterial monomer; evenly mix intermediate 2, acrylic acid chloride, potassium carbonate and acetone, and react at a speed of 80 r / min and a temperature of 65° C. for 15 hours to obtain a modified ligand;

[0053] Step A2: dissolving the modified ligand in ethanol, soaking the modified base fabric therein, ultrasonically treating for 10 min at a frequency of 30 kHz, a temperature of 65° C., and a pH value of 8, adding neodymium trichloride hexahydrate, and ultrasonically treating for 7 h, taking out and drying, forming a reinforced antibacterial layer on the surface of the modified base fabric, and obtaining a pretreated base fabric;

[0054] Step A3: Evenly mix the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane and ethanol, immerse the pretreated base fabric therein, perform ultrasonic treatment for 10 min at a frequency of 30 kHz and a temperature of 25°C, add potassium persulfate, perform ultrasonic treatment for 5 min, take out the pretreated base fabric, and perform heat preservation treatment for 3 h at a temperature of 75°C to form a protective layer on the surface of the pretreated base fabric, thereby obtaining a negative ion antibacterial polyester fiber composite fabric.

[0055] The molar ratio of o-aminothiophenol, 4-pyridinecarboxaldehyde and ammonium chloride in step A1 is 3:3:1, the usage ratio of intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile is 1 mmol:1 mmol:8 mL, and the molar ratio of intermediate 2, acrylic acid chloride and potassium carbonate is 1:1:1.1.

[0056] The amount ratio of the modified ligand, ethanol and neodymium trichloride hexahydrate described in step A2 is 5mmo l:10mL:3mmol.

[0057] The amount ratio of the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane, ethanol and potassium persulfate described in step A3 is 2.3g:18g:20g:1.2g:120mL:0.1g.

[0058] The modified base fabric is made by the following steps:

[0059] Step B1: p-Hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and ammonia water are mixed, and the mixture is reacted at a speed of 150 r / min and a temperature of 55° C. for 10 hours to obtain intermediate 2. Intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone are uniformly mixed, and the mixture is reacted at a speed of 80 r / min and a temperature of 65° C. for 15 hours to obtain intermediate 3. Intermediate 3, sodium methoxide, ethanol and tetrahydrofuran are mixed, nitrogen is introduced for protection, and the mixture is reacted at a speed of 300 r / min and a temperature of 25° C. for 3 hours to obtain a modifier;

[0060] Step B2: the modifier, itaconic acid, benzoin dimethyl ether and DMF are mixed evenly, and the reaction is carried out for 1.5 hours at a speed of 80 r / min, a temperature of 25° C. and irradiation with 365 nm ultraviolet light to obtain a modified monomer; terephthalic acid, the modified monomer, ethylene glycol, antimony trioxide and triphenyl phosphite are mixed evenly, and the reaction is carried out for 2 hours at a speed of 80 r / min and a temperature of 180° C., and the temperature is raised to 240° C. and the reaction is carried out for 5 hours at a vacuum degree of 0.5 MPa, and the temperature is raised to 280° C. and the reaction is carried out for 30 minutes at a vacuum degree of 90 Pa to obtain a modified polyester;

[0061] Step B3: The modified polyester and tourmaline powder are mixed and added into an extruder, melt-extruded and spun at a temperature of 290°C to obtain polyester fiber, and the polyester fiber and cotton fiber are subjected to cotton grabbing, cotton blending, cotton opening, cotton feeding, cotton rolling, cotton carding, cotton drawing and roving treatment to obtain composite roving, and the composite roving is weft-knitted with double rib to obtain a modified base cloth.

[0062] The amount ratio of p-hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and ammonia water described in step B1 is 4mmol:8mmol:15mmol:20mL:10mL, the mass fraction of ammonia water is 30%, the amount ratio of intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone is 5mmol:5mmol:10mmol:40mL, and the amount ratio of intermediate 3, sodium methoxide, ethanol and tetrahydrofuran is 1mmol:2mmol:2mL:2mL.

[0063] The molar ratio of the modifier and itaconic acid described in step B2 is 1:1, the amount of benzoin dimethyl ether is 1% of the total mass of the modifier and itaconic acid, the molar ratio of phthalic acid, modified monomer and ethylene glycol is 1.5:0.5:2.4, the amount of antimony trioxide is 1‰ of the mass of phthalic acid and modified monomer, and the amount of triphenyl phosphite is 1‰ of the mass of phthalic acid and modified monomer.

[0064] The mass ratio of the modified polyester and tourmaline powder described in step B3 is 100:10, and the mass ratio of the polyester fiber and the cotton fiber is 4:3.

[0065] Comparative Example 1: Compared with Example 1, no antibacterial monomer was added in this comparative example, and the remaining steps were the same.

[0066] Comparative Example 2: Compared with Example 1, no tourmaline powder was added to this comparative example, and the remaining steps were the same.

[0067] Comparative Example 3: Compared with Example 1, tetravinylsilane was not added in this comparative example, and the remaining steps were the same.

[0068] Comparative Example 4: Compared with Example 1, this comparative example uses itaconic acid instead of the modified monomer, and the prepared modified base fabric replaces the pretreated base fabric, and the other steps are the same.

[0069] The composite fabrics prepared in Examples 1-3 and Comparative Examples 1-3 were made into 5mmx5mm samples, and the antibacterial performance of the fabrics to be tested was tested with reference to the standard GB / T20944.3-2008. Gram-positive bacteria Staphylococcus aureus (ATCC6538) and Gram-negative bacteria Escherichia coli (ATCC25922) were selected as test bacteria to detect the antibacterial effect. The composite fabrics were soaked in water for 10 minutes, then dried, and the soaking was repeated 50 times to detect the antibacterial effect. The test results are shown in Table 1 below.

[0070] Table 1

[0071]

[0072]

[0073] It can be seen from Table 1 above that the present application has a very good antibacterial effect, and the antibacterial effect does not decrease significantly after washing.

[0074] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A negative ion antibacterial polyester fiber composite fabric, characterized by: The composite fabric comprises a modified base fabric, a reinforced antibacterial layer and a protective layer. The surface of the modified base fabric is provided with a reinforced antibacterial layer, and the surface of the reinforced antibacterial layer is provided with a protective layer.

2. The production process of a negative ion antibacterial polyester fiber composite fabric according to claim 1, characterized in that: The specific steps include: Step A1: o-aminothiophenol, 4-pyridinecarboxaldehyde, ammonium chloride and ethanol are mixed and reacted to obtain intermediate 1, intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile are mixed and reacted to obtain an antibacterial monomer, and intermediate 2, acrylic acid chloride, potassium carbonate and acetone are mixed and reacted to obtain a modified ligand; Step A2: dissolving the modified ligand in ethanol, immersing the modified base fabric therein, subjecting the base fabric to ultrasonic treatment, adding neodymium trichloride hexahydrate, taking out the base fabric after ultrasonic treatment, and drying the base fabric to form a reinforced antibacterial layer on the surface of the modified base fabric, thereby obtaining a pretreated base fabric; Step A3: evenly mix the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane and ethanol, immerse the pretreated base fabric therein, perform ultrasonic treatment, add potassium persulfate, take out the pretreated base fabric after ultrasonic treatment, perform heat preservation treatment, form a protective layer on the surface of the pretreated base fabric, and obtain a negative ion antibacterial polyester fiber composite fabric.

3. The production process of a negative ion antibacterial polyester fiber composite fabric according to claim 2, characterized in that: The molar ratio of o-aminothiophenol, 4-pyridinecarboxaldehyde and ammonium chloride in step A1 is 3:3:1, the usage ratio of intermediate 1, ethyl 2-bromomethylacrylate and acetonitrile is 1 mmol:1 mmol:8 mL, and the molar ratio of intermediate 2, acrylic acid chloride and potassium carbonate is 1:1:1.

1.

4. The production process of a negative ion antibacterial polyester fiber composite fabric according to claim 2, characterized in that: The modified ligand, ethanol and neodymium trichloride hexahydrate described in step A2 are used in a ratio of 5 mmol:10 mL:3 mmol.

5. The production process of a negative ion antibacterial polyester fiber composite fabric according to claim 2, characterized in that: The amount ratio of the antibacterial monomer, methyl methacrylate, n-butyl acrylate, tetravinylsilane, ethanol and potassium persulfate described in step A3 is 2.3g:18g:20g:1.2g:120mL:0.1g.

6. The production process of a negative ion antibacterial polyester fiber composite fabric according to claim 2, characterized in that: The modified base fabric is made by the following steps: Step B1: p-Hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and aqueous ammonia are mixed and reacted to obtain intermediate 2; intermediate 2, S-(2-bromoethyl)ethylthioate, potassium carbonate and acetone are mixed and reacted to obtain intermediate 3; intermediate 3, sodium methoxide, ethanol and tetrahydrofuran are mixed, nitrogen protection is introduced, and reaction is carried out to obtain a modifier; Step B2: mixing a modifier, itaconic acid, benzoin dimethyl ether and DMF to obtain a modified monomer, and mixing terephthalic acid, the modified monomer, ethylene glycol, antimony trioxide and triphenyl phosphite to obtain a modified polyester; Step B3: The modified polyester and tourmaline powder are mixed and added into an extruder, melt-extruded and spun to obtain polyester fiber, the polyester fiber and cotton fiber are subjected to cotton grabbing, cotton blending, cotton opening, cotton feeding, cotton rolling, cotton carding, cotton drawing and roving treatment to obtain composite roving, the composite roving is weft-knitted double rib weave to obtain a modified base cloth.

7. The production process of a negative ion antibacterial polyester fiber composite fabric according to claim 6, characterized in that: The amount ratio of p-hydroxybenzaldehyde, 2-acetylpyridine, potassium hydroxide, ethanol and ammonia water described in step B1 is 4mmol:8mmol:15mmol:20mL:10mL, the amount ratio of intermediate 2, S-(2-bromoethyl)ethanethioate, potassium carbonate and acetone is 5mmol:5mmol:10mmol:40mL, and the amount ratio of intermediate 3, sodium methoxide, ethanol and tetrahydrofuran is 1mmol:2mmol:2mL:2mL.

8. The production process of a negative ion antibacterial polyester fiber composite fabric according to claim 6, characterized in that: The molar ratio of the modifier described in step B2 to itaconic acid is 1:1, and the molar ratio of phthalic acid, modified monomer and ethylene glycol is 1.5:0.5:2.

4.

9. The production process of a negative ion antibacterial polyester fiber composite fabric according to claim 6, characterized in that: The mass ratio of the modified polyester and tourmaline powder in step B3 is 100:8-10, and the mass ratio of the polyester fiber and the cotton fiber is 4:3.

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